Liquid compositions comprising a nitrogenous polymer



Patented Mar. 5, 1957 Research Institute, Inc., New York, pages 28, 29,876 I 2,784,166 and 877): LIQUID COMPOSITIONS COMPRISING A 1.Polymerizes at 70 C.

NITROGENGUS POLYMER 2. Due to low polymerization temperature there is nowicking. fi g' ggffifig ig gg g g gg g m gggg 3. Accordingly, it isapplicable to fiber as well as fabric.

amid Company, New York, N. Y., a corporation of prflduces a non'sweumgfiber- Maine 5. Gives good wet strengths to the fabric.

6. Gives nonshrinking effect. No Drawmg' APphcatlon February 1954 7.Gives improved resistance to alkali solubility and to Serial No. 408,574laundering 17 Claims. (Cl. 260-29.2) 8. Improves dye afi'inity and givesbetter light fastness and wash fastness. V v 9. Probably can go to avery low swelling fiber without This invention relates broadly to newand useful liquid 5 lowering abrasion resistance compositions comprisinga nitroge o s P Y More 10. Water stable impressions can be made fornovelty particularly the invention is concerned with liquid cO mfi t sch as crepes. positions comprising, by weight, (1) a major Proportion11. Imparts resilience and good handle to fiber and (that is, more than50%) of water and (2) a minor 20 to ortion (that is, less than 50%) of apolymer ob-' ain ed by polymerizing, in acidic water, a polyethylenePage 876 of .thls same pubhcfitlonjt further stated melamine which is apolyamino-s-triazine wherein at least wlth, regard 9 methyloene melamme:Thls Product Poly two of the amino nitrogen atoms each has one ethylenemerizes readily at 70 C. before moisture 1s evaporated fabric.

group attached thereto instead of the two hydrogen atoms. one featurenot suflicienfly established is wllether By this definition ofpolyethylene melamine is meant 5 the monomer can be established in apractlcal way. By specifically diethylene melamine, the formula forwhich is thls latter comment was meant that was not known If triethylenemelamine was sufiiciently stable to storage to be commerciallypracticable.

I NEQ To the best of our knowledge and belief a polyethylene melamine,specifically triethylene melamine, was not used T in commercial practiceas a textile-treating agent prior H,c\ ll\ 1? /CH2 to our inventiondespite the aforementioned advantages N(J; CN I of the material.Although high cost may have been one important factor which contributedto its non-commercial exploitation and use, our experience has indicatedthat another important factor was the difiiculty in obtaining solutionsof the monomer which would have adequate and methylene melamme theformula for which Is storage stability and which could be inhibitedagainst premature polymerization so that uniform finishes could H 0 beapplied to the textile material to be treated.

\ I The present invention is based on our discovery that the faforementioned advantages flowing from the use of solu- C tions ofmonomeric polyethylene melamine, specifically H2O CH2 monomericdiethylene melamine and triethylene mela- I! L mine, can be attained andthe problem of storage insta- "bility of such solutions until used, orthe necessity of H20 N CH:

adding a polymerization inhibitor thereto, can be obviated by formingliquid compositions of the kind broadly described in the first paragraphof this specification and more Both diethylene melamine and triethylenemelamine are fully hereafter.

known compounds, and methods for their preparation and The liquidcompositions of this invention are produced their characteristicproperties are described in the prior by admixing (1) acidic water and(2) diethylene melaart, e. g., in Patent Nos. 2,520,619 and 2,653,934.mine or triethylene melamine, or mixtures of diethylene It was suggestedprior to our invention that triethylene melamine and triethylenemelamine in any proportions, melamine be used as a textile-treatingagent, for which, 5 and polymerizing the polyethylene melamine or melaifcapable of being stabilized in monomeric form, the "mines of (2) whileadmixed with the acidic water of following advantages were claimed(reference: Synthetic (1). If the liquid compositions as initiallyproduced are Fiber Developments in Germany, P. B. 7416. Report preparedby the synthetic Fibers Team of the Technical water and a minorproportion of a polymer obtained by Industrial Intelligence Committee,compiled and edited polymerizing in acidic water the polyethylenemelamine by Le Roy H. Smith, published in 1946 by Technical or melaminesof (2), they are adjusted so that they are not constituted of, byweight, a major proportion of so constitutedafter initial preparation ofthe polymer in the acidicwater. This adjustment maytakeplaceatanytsuitable time prior to use of the material, for instance eitherimmediately after preparation, or after a filtering step prior toshipment by the manufacturer or shipper to the user, or shortly beforebeing used. The solution is adjusted, if necessary, prior to use to thepH conditions which give optimum results when the solution is applied tothe textile or other material to be treated.

We are unable to explain with certainty with a polyethylene melaminewhen polymerized in acidic water should yield a solution which isrelatively stable on storage, that is, as compared with correspondingsolutions of monomeric polyethylene melamine, while at the same timeproviding a solution which, when used as a textilq treating-agent,"paper-treating ag'ent and in'other applications, gives beneficialresults and advantages which, it was believed prior to ourinventiongcould .belobtained only from the use of 7 a solution ofalmonomeric poly.- ethylene melamine, specifically monomeric triethylenemelamine, One possibleexplanation is that the polymer produced in thisway is of thelinear type and iswatersoluble, or if not Water-solublethen it,is.;at leastreadily water-dispersible to form particles ofcolloidal or nearcolloidal size or nature, One possibletand logicaltheoretical explanation for the formation of suchIaspolymeris shown bythe following equations, talginglriethylene melamine as illustrative ofthe polyethylene-,melamine employed:

For purpose ,of simplicity Equation IV has been written to show merelythe dimeras the polymerwhich is formed; but obviously the recurring unitstructure appearing with in the brackets N p n containing the desiredamount of acid. The temperature of admixture. of the acidic water andpolyethylene melamine may be considerably varied, as desired or asconditions may require, optimum results being obtained when thetemperature is not less than about 10 C. and not higher than about 45 C.Normal room temperature conditions of 2030 C. generally are satisfactoryfor efiecting reaction between the acidic water and the monomericpolyethylene melamine to produce the desired polymer of the desiredmolecular weight and particle size within a reasonable period of time.

The kind of acid or acidic substance which is employed does not appearto be critical. For economical and other reasons some are obviouslypreferred over others, among which may be mentioned acetic acid,phosphoric acid and hydrochloric acid. Examples of other organic andinorganic acids that can be used include: sulfuric, sulfonic,phosphinic, phosphonic, nitric, hydrobromic, sulfurous, phosphorous,alkyl phosphoric, oxalic, malonic, succinic, propionic, lactic, citric,hydrozyacetic, fl-hydroxypropionic, butyric, valeric, chloroacetic,acrylic, crotonic, 'phthalic, etc., as well as mixtures of variousorganic acids, or of various inorganic acids, or of organic andinorganic acids. Acid salts can be used instead of the acids themselves,if desired, for instance sodium acid sulfate, monosodium phosphate,monosodium phthalate, etc., as well as mixtures of acid salts, ormixtures of an acid salt and an organic and/ or inorganic acid.

Theamount of acid employed will vary considerably depending upon theparticular acid employed, polyethylene melamine employed, time,temperature and other conditions of reaction, method and rapidity ofadmixture, extent of polymerization desired and particle size andsolubility characteristics of the polymer and other infiuencing factors.Ordinarily, however, the amount of acid employed corresponds to from0.03 to 3 moles (about 0.03 to about 3 moles) thereof per mole ofpolyethylene melamine, that is, per mole of diethylene melamine, ortriethylene melamine, or mixture of diethylene melamine and triethylenemelamine in any proportions. Good results have been obtained using fromabout 0.06 to about 2.0 moles of acid, specifically acetic acid,hydrochloric acid and phosphoric acid, per mole of polyethylenemelamine. The amount of acid employed and the time and method ofadmixture of the acidic water and polyethylene melamine obviously shouldhe so correlated as to avoid gelation of the admixture.

The liquid compositions of this invention are especially suitable foruse as textile-treating agents for improving the useful properties ofsuch textiles as cotton, viscose rayons, wool, etc. For suchapplications, as well as for others, the polymer obtained bypolymerizing the polyethylene melamine in acidic water advantageouslyconstitutes from about 1% to about 30%, more particularly from about 2%to about 15%, by weight of the total amount of said polymer and of waterwhich is present in the liquid composition. In general, the textiles areimmersed in the liquid composition during the treating process, and thepolyethylene melamine polymer ordinarily exhausts upon the textile in apercentage corresponding to or approximating the percentage of polymerwhich is present in the composition.

In order that those skilled in the-art maybetter understand howourinvention can be carried into eifect, the following examples aregiven by way of illustrationvand not by way of limitation All parts andpercentages are by weight' Example 1 per-mole of-triethylene melamine.From an initial pH at 8.5 the pl-I is decreased to 3.4 by this amountofacid. More detailed data are given below:

Upon plotting the results (pH v. cc. of 0.5 N HCl), it is found thatthere is a sharp change in the inflection of the curve at a pH of 5.1,that is, after about 25 cc. of 0.5 N HCl have been added. This isindicative that the polyethylene melamine has undergone reaction. Thetheoretical equivalence point is 49 cc. of 0.5 N HCl (pH of 4.0).

The solution is filtered to remove any suspended or water-insolublematter. The filtered solution is suitable for use as a beater additivein the formation of paper, thereby to obtain a paper having improvedwet-strength characteristics as compared with similarly formed paper inwhich no triethylene melamine has been incorporated.

Example 2 Same as Example 1 with the exception that diethylene melamineis used instead of triethylene melamine. Similar end results areobtained.

Example 3 Two separate solutions are prepared, each by dissolving gramsof triethylene melamine in 50 grams of water. One solution (A) istitrated electrometrically with 0.5 N aqueous hydrochloric acid to a pHof 4.0. This corresponds to about 1.34 moles of acid per mole oftriethylene melamine. More detailed data are given below:

The other solution (B) of 10 grams of triethylene melamine dissolved in50 grams of water is mixed with 98 cc. of 0.5 N aqueous hydrochloricacid, yielding a solution containing about 6.33% by weight oftriethylene melamine and having a pH of 4.6. This corresponds to about1.0 mole of acid per mole of triethylene melamine.

Both of the aforementioned solutions can be used directly, that is,without filtration, as beater additives in the formation of paper. Usingsolution (B) in an amount such that the amount of triethylene melaminepresent is equivalent to 3% by weight, based on the dry weight of thepaper stock, a paper having a dry strength of 26 lbs. per inch and a wetstrength of 2 lbs. per inch is obtained. Higher wet-strength papers canbe pro- 6 duced by increasing the concentration of triethylene melamineemployed and/or by employing other acid solutions (true solutions orcolloidal solutions) of the polyethylene melamine, specificallytriethylene melamine.

Example 4 A 10-gram sample of triethylene melamine is dissolved in 50grams of water and titrated electrometrically with 0.52 N aqueous aceticacid solution, using a total of 149.5 cc. of the latter.,. Thiscorresponds to about 1.58 moles of acid per mole of triethylenemelamine. There is a sharp drop in pH with the addition of the first 5cc. of acetic acid solution, after which the pH changes very graduallyuntil the theoretical equivalence point is reached upon adding 98 cc. ofreagent (pH of the solution after thisamount of reagent has been addedis 4.2). More detailed data aregiven below:

This solution has good strorage stability and is suitable for use as afinishing agent for viscose rayons in the form of staple fibers orcontinuous filament yarns, or in treating fabrics made therefrom, inorder to impart improved water-repellency thereto and otherwise toimprove their properties.

Example 5 A IO-gram sample of triethylene melamine is dissolved in 50grams of water and titrated electrometrically with an aqueous phosphoricacid solution containing 32.66 grams of phosphoric acid per liter ofsolution. More detailed data are given below:

Cc. of phosphoric acid solution added: pH

None 8.9 1 6.4 2 6.25 5 5.8

When another 5 cc. of acid is added, the solution gels. This gel willnot disperse in the water.

Example 6 Example 5 is repeated, but using an aqueous phosphoric acidsolution containing 16.33 grams of 85% phosphoric acid per liter ofsolution. More detailed data are given below:

Co. of phosphoric acid solution added: pH

None 8.7 5 6.1 10 5.85 15 5.65 20 5.3

When another 2.5 cc. of acid is added, the solution gels. This gel willnot disperse in water.

Example :7

group attached thereto instead of the two hydrogen atoms: n om W th-(in) ic wa nti he a Po y melamine has polymerizedto the desired degree.

2. A liquid composition asin claim 1 wherein the acidic water in whichthe polyethylene melamine is polymerized contains an acid in an amountcorresponding to from 0.013 to 3' moles thereof per mole of polyethylenemelamine.

3: A liquid composition as in claim 1 wherein the polyethylene melamineof (a) is diethylene melamine, the formula for which is 4. A liquidcomposition as in claim 1 wherein the polyethylene melamine of-(a) istriethylene melamine, the formula for which is 5. A liquid compositionas in claim 1 wherein the acid employed in producing the acidic water of(b) is hydrochloric acid.

6. A liquid composition as in claim 1 wherein the acid employed inproducing the acidic water of (b) is phosphoric acid.

7. A liquid composition as in claim 1 wherein the acid employed inproducing'the acidic water of (b) is acetic acid.

A-.. uidco position in cla m. wherein he poly.-

mer of (2) constituteslffrom about 1% to about 3 0% .h y v weight of thetotal of (1) and (2) I 9.; An aqueous hydrochloric acidtsolutionof apolymer obtained ,by, contactingtriethylene. melaminedissolved in waterwhile, hydrochloric. acidisadmixedtherewith, said polymer. constituting.fromv aboutv 1% to. about. 30% by weight. of. the said, hydrochloric.acid, solution.

1.0- An .aqueouslphosphoric. acidsolutionot apolymer b inedhy contacing. riethylene. m lamine. i s lve in water while phosphoric acid isadmixed therewith, said P y er. onstituting frnm.abput,1%. to about 30%by Weightot the said phosphoricacid olution.

1.1- An nneous ceticv acidsolution or. apolymer obn i y contac ing rithylene. melamine dissolved in water whileacetic acid isadmixedtherewith, said, polymer constituting fromabout 1% toabout 30% byweight of the saidacetic acidso-lution.

12, The method which. comprises contacting, (1) a polyethylene melaminewhich is a polyamino-s-triazine wherein at. least two of theaminonitrogen atoms each has one ethylene group attached thereto instead ofthe two hydrogen atoms with. (2) acidic water, and maintaining the saidpolyethylene melamine of (l) in Contact with the acidic water of. (2)until the polyethylene melamine has polymerized to the desired degree.

13. A method as in claim 12 wherein the acid employed in producing theacidic water. is hydrochloric acid.

14. 'A method as in claim 12 wherein the acid employed inproducing theacidic Water is phosphoric acid.

15. A method as in claim 12 wherein the acid employed in producing theacidic water is acetic acid.

'16. Amethod as inclaim 12 wherein the polyethylene melamine istriethylene melamine and the acidic water contains acid in an amountcorresponding to from 0.03

to 3 moles thereof per mole oftriethylene melamine.

17. The method which comprises admixing (1) a polyethylene'melaminewhich is a polyamino-s-triazine wherein at least two of the aminonitrogen atoms each has one ethylene group attached thereto instead ofthe two hydrogen atoms and (2) acidic water, and maintaining theresulting admixture at a temperature within the range of about 10 C. toabout C. until the polyethylene melamine has polymerized to a polymerofthe desired a molecular weight and particle size.

References Cited in the-file of this patent German Synthetic FiberDevelopments, by Smith, published 1946 by Textile Research InstituteInc., New York, N. Y., page 876.

ay-M

1. A LIQUID COMPOSITION COMPRISING BY WEIGHT, (1) A MAJOR PROPORTION OFWATER AND (2) A MINOR PROPORTION OF A POLYMER OBTAINED BY MAINTAINING(A) A POLYETHYLENE MELAMINE WHICH IS A POLYMINO-S-TRAZINE WHEREIN ATLEAST TWO OF THE AMINO NITROGEN ATOMS EACH HAS ONE ETHYLENE GROUPATTACHED THERETO INSTEAD OF THE TWO HYDROGEN ATOMS IN CONTACT WITH (B)ACIDIC WATER UNTIL THE SAID POLYETHYLENE MELAMINE HAS POLYMERIZED TO THEDESIRED DEGREE.